CN113862770A - Method for preparing patterned electrode by deplating process - Google Patents

Method for preparing patterned electrode by deplating process Download PDF

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Publication number
CN113862770A
CN113862770A CN202111140314.8A CN202111140314A CN113862770A CN 113862770 A CN113862770 A CN 113862770A CN 202111140314 A CN202111140314 A CN 202111140314A CN 113862770 A CN113862770 A CN 113862770A
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metal
electrode
photoresist
layer
metal film
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CN113862770B (en
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邓元
李冉冉
张玮峰
华小社
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Hangzhou Innovation Research Institute of Beihang University
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Hangzhou Innovation Research Institute of Beihang University
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00Electrolytic stripping of metallic layers or coatings
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/16Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/18Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/12Semiconductors
    • C25D7/123Semiconductors first coated with a seed layer or a conductive layer
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor

Abstract

The invention discloses a method for preparing a patterned electrode by adopting a deplating process and the patterned electrode, and the method comprises the following steps: sputtering a conductive seed layer on the surface insulating substrate; electroplating a metal film on the sputtered conductive seed layer; spin-coating photoresist on the surface of the metal film, and etching an electrode pattern on the surface of the metal film by adopting a photoetching method; processing by adopting a deplating method, so that the metal film and the conductive seed layer which are not protected by the photoresist are dissolved by reaction, and the part with the photoresist is reserved; and (4) carrying out ultrasonic cleaning after deplating, and removing photoresist and metal debris residues to obtain the patterned electrode. The invention saves the wet etching link, thereby avoiding various problems caused by the wet etching.

Description

Method for preparing patterned electrode by deplating process
Technical Field
The invention relates to the field of electrode processing and manufacturing, in particular to a method for preparing a patterned electrode by adopting a deplating process and the patterned electrode.
Background
At present, the process flow of electroplating-photoetching-wet etching is mostly adopted for producing thick film patterned electrodes (the thickness of the electrode is more than 10 mu m) in large area. Although the process can ensure the pattern precision of the electrode, the process steps are numerous, the types of required chemicals are numerous, and a large amount of chemical waste liquid is generated in the process of wet etching the metal film. The direct discharge of the waste liquid can seriously pollute the environment, the waste liquid treatment wastes time and labor, and the production cost is increased. In addition, most etching liquid used in wet etching contains acidic and alkaline solutions with strong corrosivity, and when metal is etched, the etching liquid can also etch the substrate, damage the crystal structure on the surface of the substrate, increase the roughness and further possibly cause serious influence on the performance of a device.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a method for preparing a patterned electrode by adopting a deplating process and the patterned electrode, and the method omits a wet etching link so as to avoid various problems caused by wet etching.
The invention discloses a method for preparing a patterned electrode by adopting a deplating process, which adopts the technical scheme that the method comprises the following steps:
sputtering a conductive seed layer on the surface insulating substrate;
electroplating a metal film on the sputtered conductive seed layer;
spin-coating photoresist on the surface of the metal film, and etching an electrode pattern on the surface of the metal film by adopting a photoetching method;
processing by adopting a deplating method, so that the metal film and the conductive seed layer which are not protected by the photoresist are dissolved by reaction, and the part with the photoresist is reserved;
and (4) carrying out ultrasonic cleaning after deplating, and removing photoresist and metal debris residues to obtain the patterned electrode.
Further, the surface insulating substrate is an AlN substrate or a SiC substrateWith SiO at the bottom or surface2A silicon wafer substrate of an insulating layer.
Further, the conductive seed layer has a three-layer structure, which includes an adhesion metal layer below and in direct contact with the surface insulating substrate, a heat and conductive metal layer above, and a transition metal layer between the adhesion metal layer and the heat and conductive metal layer.
Further, the adhesion metal layer is Cr, the heat and electricity conductive metal layer is Cu, and the transition metal layer is Ti.
Further, the process of electroplating the metal film on the sputtered conductive seed layer is to use the surface insulating substrate on which the conductive seed layer is sputtered as a counter electrode, use the metal sheet as a working electrode, put into a metal electrolyte for electroplating, and plate the metal film.
Further, the metal includes copper, chromium, or titanium.
Furthermore, the method for spin-coating the photoresist on the surface of the metal film is two-stage spin coating, wherein low-rotation-speed spin coating is firstly performed, and then high-rotation-speed spin coating is performed.
Further, the treatment by the deplating method is performed by taking the surface insulating substrate on which the electrode pattern is photoetched as a working electrode and a metal piece as a counter electrode, placing the working electrode and the metal piece into a metal electrolyte, and applying a battery opposite to that in the electroplating to deplate.
Further, ultrasonic cleaning was performed with acetone after deplating.
The invention also discloses a patterned electrode prepared by the method.
The invention has the following beneficial effects: the patterned electrode is prepared by using the electroplating-photoetching-deplating method, and compared with the traditional electroplating-photoetching-wet etching preparation method, the wet etching link is omitted. The electroplating-photoetching-deplating process avoids using etching liquid polluting the environment on the basis of keeping the pattern precision, greatly simplifies the preparation flow, is convenient to operate, saves time and reduces the cost. In addition, the chemical corrosion of the etching liquid is avoided, so that the surface structure of the substrate is complete and the substrate still keeps a smooth and bright state.
Drawings
FIG. 1 is a schematic diagram of an exemplary process flow;
FIG. 2 is a photograph of a digital camera with an entire patterned copper electrode in accordance with an embodiment;
fig. 3 is an optical microscope photograph of a single patterned copper electrode in an example.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples.
The core of the invention is to process the photoetched electrode pattern by adopting a deplating process, which comprises the following steps:
sputtering a conductive seed layer on the surface insulating substrate;
electroplating a metal film on the sputtered conductive seed layer;
spin-coating photoresist on the surface of the metal film, and etching an electrode pattern on the surface of the metal film by adopting a photoetching method;
processing by adopting a deplating method, so that the metal film and the conductive seed layer which are not protected by the photoresist are dissolved by reaction, and the part with the photoresist is reserved;
and (4) carrying out ultrasonic cleaning after deplating, and removing photoresist and metal debris residues to obtain the patterned electrode.
The principle of the invention is as follows: the deplating is the reverse process of electroplating, and when the patterned substrate plated with a metal film is used as a working electrode (anode), the metal parts without the protection of the photoresist lose electrons and become metal ions which are dissolved in the electroplating solution. After the surface metal is dissolved, the conductive seed layer metal can lose electrons and be dissolved, and the metal protected by the photoresist is remained, so that the purpose of electrode patterning can be realized. In order to reduce the influence of lateral etching, the reaction time can be reduced and the electrode pattern precision can be improved by increasing the current density between the working electrode and the counter electrode.
The method can be used for preparing electrodes of common metals such as copper, chromium, titanium and the like, and the surface insulating substrate can be AlN substrate, SiC substrate and SiO on the surface2Silicon wafer substrate or other surface insulating substrate of the insulating layer. Because the wet etching link is saved, the method isOn the basis of keeping the pattern precision, the etching liquid polluting the environment is avoided, the preparation flow is greatly simplified, the operation is convenient, the time is saved, and the cost is reduced. In addition, the chemical corrosion of the etching liquid is avoided, so that the surface structure of the substrate is complete and the substrate still keeps a smooth and bright state.
The following are illustrated by specific examples:
example 1
The process flow of this example is shown in fig. 1, wherein a seed layer of Cr/Ti/Cu is magnetron sputtered on an AlN substrate, and electroplated copper is used as a metal film to prepare a patterned electrode.
Step one, sputtering a conductive seed layer on a substrate
Cutting the AlN substrate into a proper size, putting the AlN substrate into alcohol for 30 min by ultrasonic treatment, washing off the dust and other adherends on the surface, taking out the AlN substrate and drying the AlN substrate by a nitrogen gun. And putting the AlN substrate into a high-vacuum magnetron sputtering system to sputter a conductive seed layer.
In this embodiment, the conductive seed layer has a three-layer structure, which includes an adhesion metal layer below and in direct contact with the surface insulating substrate, a heat and conductive metal layer above, and a transition metal layer between the adhesion metal layer and the heat and conductive metal layer, specifically, Cr/Ti/Cu, where Cr is in direct contact with AlN as an adhesion metal, and Cu has high thermal and electrical conductivity and serves as a heat and conductive metal layer. Due to the large difference in thermal expansion rates between Cr and Cu (6.2 x 10^ respectively)-6 K-1,17.5 * 10^-6 K-1) Ti as transition layer metal (thermal expansion rate of 12.2 x 10^ 10)-6 K-1) And the stress problem caused by overlarge thermal expansion coefficient difference is reduced. The co-sputtering process is carried out between every two metal films to increase the connection strength between the films.
The specific parameters of sputtering Cr/Ti/Cu are as follows: the sputtering vacuum degree is 2.36E-4 Torr, the pre-sputtering Ar gas flow is 15 sccm, the target power is 50W, the pre-sputtering time is 30 s, the Ar gas flow is 20 sccm when starting sputtering, and the target power is 120W. The sputtering time is respectively 4 min, 9 min and 10 min, and finally the conductive seed layers of 50 nm Cr, 50 nm Ti and 150 nm Cu are obtained. For the co-sputtering process between films, the sputtering power of the two metal targets is slowly transited from 100W/100W and 80W/120W to only one metal.
Step two, electroplating the metal thick film
Taking the AlN sputtered with the conductive seed layer as a counter electrode and a pure copper sheet as a working electrode, and putting the working electrode into a copper electrolyte, wherein the formula of the copper electrolyte is as follows: 220 g/L of copper sulfate pentahydrate, 60 g/L of concentrated sulfuric acid and 60 mg/L of concentrated hydrochloric acid. The current density is 0.75 to 1.5A/dm2The deposition time is 20-50 min, and a copper thick film electrode with a thickness of 2-20 μm can be obtained.
Step three, photoetching electrode pattern
And spin-coating photoresist on the surface of the electrochemical deposition metal film. The type of the used photoresist is AZ4620, the photoresist homogenizing rate is two-section type photoresist homogenizing, the photoresist is firstly homogenized at a low rotating speed of 500 rpm for 5 s, the rotating speed acceleration is 500 rpm/s, then the photoresist is homogenized at a high rotating speed of 2000 rpm for 60 s, the rotating speed acceleration is 2000 rpm/s, and the photoresist homogenizing thickness is about 12 mu m. Baking at 110 deg.C for 180 s, and cooling for 3 min.
The spin-coated samples were placed into a high precision maskless lithography system, model number MicroWriter ML3, and the positions to be exposed were found under a microscope and autofocus. Introducing the drawn electrode pattern into a photoetching system, wherein the used laser wavelength is 405 nm, the exposure resolution is 1 mu m, and the exposure dose is 650 mJ/cm2After the parameters are set, exposure is performed. After exposure, developing for 12 min by using MF-319 developing solution, fixing for 30 s by using deionized water, and then drying by using a nitrogen gun. Thus obtaining the exposed electrode pattern.
Step four, deplating
Placing the patterned AlN substrate with copper plated on the surface as a working electrode and a pure copper sheet as a counter electrode into a copper electroplating solution, applying an electric field opposite to that in copper electroplating, and applying a current density of 6-15A/dm2And after the time is about 60-180 s, the copper thick film without the photoresist protection part and the seed layer are dissolved by reaction, and the part with the photoresist is reserved.
Step five, acetone ultrasonic cleaning
And putting the deplated sample into acetone, and dissolving and washing the photoresist by the acetone. The residual metal fragments fall off under the action of ultrasonic waves, and after deionized water is sprayed and washed, nitrogen is blown to dry. A patterned electrode pattern is obtained. The digital camera photograph and the optical microscope photograph of the patterned copper electrode are shown in fig. 2 and 3, respectively.
The above description is only a preferred embodiment of the present invention, and should not be construed as limiting the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims (10)

1. A method of making a patterned electrode using a deplating process, comprising the steps of:
sputtering a conductive seed layer on the surface insulating substrate;
electroplating a metal film on the sputtered conductive seed layer;
spin-coating photoresist on the surface of the metal film, and etching an electrode pattern on the surface of the metal film by adopting a photoetching method;
processing by adopting a deplating method, so that the metal film and the conductive seed layer which are not protected by the photoresist are dissolved by reaction, and the part with the photoresist is reserved;
and (4) carrying out ultrasonic cleaning after deplating, and removing photoresist and metal debris residues to obtain the patterned electrode.
2. The method of claim 1, wherein the surface insulating substrate is an AlN substrate, a SiC substrate, or a SiO-surfaced substrate2A silicon wafer substrate of an insulating layer.
3. The method of claim 1, wherein the conductive seed layer has a three-layer structure including an adhesion metal layer directly contacting the surface insulating substrate, a thermal and electrical conductive metal layer above the adhesion metal layer, and a transition metal layer between the adhesion metal layer and the thermal and electrical conductive metal layer.
4. The method of claim 3, wherein the adhesion metal layer is Cr, the thermal and electrical conductive metal layer is Cu, and the transition metal layer is Ti.
5. The method of claim 1, wherein the step of electroplating the metal film on the sputtered conductive seed layer comprises electroplating in a metal electrolyte solution with the insulating substrate on the surface of the sputtered conductive seed layer as a counter electrode and the metal sheet as a working electrode to form a metal film.
6. The method of making a patterned electrode using a deplating process according to claim 5, wherein the metal comprises copper, chromium, or titanium.
7. The method of claim 1, wherein the spin coating of the photoresist on the surface of the metal film is a two-step spin coating using a low spin coating and a high spin coating.
8. The method of claim 1, wherein the step of deplating is performed by removing the patterned electrode by exposing the surface insulating substrate having the electrode pattern formed thereon to light as a working electrode and the metal sheet as a counter electrode to a metal electrolyte and applying a current opposite to that applied during the step of electroplating.
9. The method of claim 1, wherein the step of removing the patterned electrode comprises ultrasonic cleaning with acetone after the step of removing the patterned electrode.
10. A patterned electrode prepared by the method of any one of claims 1 to 9.
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CN115424542A (en) * 2022-11-03 2022-12-02 长春希达电子技术有限公司 Seamless spliced Micro-LED display panel and preparation method thereof
CN115846885A (en) * 2023-01-31 2023-03-28 东莞市湃泊科技有限公司 Method and system for manufacturing graph by laser etching

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115424542A (en) * 2022-11-03 2022-12-02 长春希达电子技术有限公司 Seamless spliced Micro-LED display panel and preparation method thereof
CN115424542B (en) * 2022-11-03 2023-02-28 长春希达电子技术有限公司 Seamless spliced Micro-LED display panel and preparation method thereof
CN115846885A (en) * 2023-01-31 2023-03-28 东莞市湃泊科技有限公司 Method and system for manufacturing graph by laser etching

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